Modeling aluminum-silicon chemistries and application to Australian acidic playa lakes as analogues for Mars

Recent Mars missions have stimulated considerable thinking about the surficial geochemical evolution of Mars. Among the major relevant findings are the presence in Meridiani Planum sediments of the mineral jarosite (a ferric sulfate salt) and related minerals that require formation from an acid-salt brine and oxidizing environment. Similar mineralogies have been observed in acidic saline lake sediments in Western Australia (WA), and these lakes have been proposed as analogues for acidic sedimentary environments on Mars. The prior version of the equilibrium chemical thermodynamic FREZCHEM model lacked Al and Si chemistries that are needed to appropriately model acidic aqueous geochemistries on Earth and Mars. The objectives of this work were to (1) add Al and Si chemistries to the FREZCHEM model, (2) extend these chemistries to low temperatures (<0 °C), if possible, and (3) use the reformulated model to investigate parallels in the mineral precipitation behavior of acidic Australian lakes and hypothetical Martian brines.FREZCHEM is an equilibrium chemical thermodynamic model parameterized for concentrated electrolyte solutions using the Pitzer approach for the temperature range from <−70 to 25 °C and the pressure range from 1 to 1000 bars. Aluminum chloride and sulfate mineral parameterizations were based on experimental data. Aluminum hydroxide and silicon mineral parameterizations were based on Gibbs free energy and enthalpy data. New aluminum and silicon parameterizations added 12 new aluminum/silicon minerals to this Na-K-Mg-Ca-Fe(II)-Fe(III)-Al-H-Cl-Br-SO₄-NO₃-OH-HCO₃-CO₃-CO₂-O₂-CH₄-Si-H₂O system that now contain 95 solid phases.There were similarities, differences, and uncertainties between Australian acidic, saline playa lakes and waters that likely led to the Burns formation salt accumulations on Mars. Both systems are similar in that they are dominated by (1) acidic, saline ground waters and sediments, (2) Ca and/or Mg sulfates, and (3) iron precipitates such as jarosite and hematite. Differences include: (1) the dominance of NaCl in many WA lakes, versus the dominance of Fe-Mg-Ca-SO₄ in Meridiani Planum, (2) excessively low K⁺ concentrations in Meridiani Planum due to jarosite precipitation, (3) higher acid production in the presence of high iron concentrations in Meridiani Planum, and probably lower rates of acid neutralization and hence, higher acidities on Mars owing to colder temperatures, and (4) lateral salt patterns in WA lakes. The WA playa lakes display significant lateral variations in mineralogy and water chemistry over short distances, reflecting the interaction of acid ground waters with neutral to alkaline lake waters derived from ponded surface runoff. Meridiani Planum observations indicate that such lateral variations are much less pronounced, pointing to the dominant influence of ground water chemistry, vertical ground water movements, and aeolian processes on the Martian surface mineralogy.     

Sedimentary iron geochemistry in acidic waterways associated with coastal lowland acid sulfate soils

We examined the solubility, mineralogy and geochemical transformations of sedimentary Fe in waterways associated with coastal lowland acid sulfate soils (CLASS). The waterways contained acidic (pH 3.26-3.54), Fe^III-rich (27-138 μM) surface water with low molar Cl:SO₄ ratios (0.086-5.73). The surficial benthic sediments had high concentrations of oxalate-extractable Fe(III) due to schwertmannite precipitation (kinetically favoured by 28-30% of aqueous surface water Fe being present as the Fe^III species). Subsurface sediments contained abundant pore-water HCO₃ (6-20 mM) and were reducing (Eh < −100 mV) with pH 6.0-6.5. The development of reducing conditions caused reductive dissolution of buried schwertmannite and goethite (formed via in situ transformation of schwertmannite). As a consequence, pore-water Fe^II concentrations were high (>2 mM) and were constrained by precipitation-dissolution of siderite. The near-neutral, reducing conditions also promoted SO₄-reduction and the formation of acid-volatile sulfide (AVS). The results show, for the first time for CLASS-associated waterways, that sedimentary AVS consisted mainly of disordered mackinawite. In the presence of abundant pore-water Fe^II, precipitation-dissolution of disordered mackinawite maintained very low (i.e. <0.1 μM) S^−II concentrations. Such low concentrations of S^−II caused slow rates for conversion of disordered mackinawite to pyrite, thereby resulting in relatively low concentrations of pyrite (<300 μmol g⁻¹ as Fe) compared to disordered mackinawite (up to 590 μmol g⁻¹ as Fe). This study shows that interactions between schwertmannite, goethite, siderite, disordered mackinawite and pyrite control the geochemical behaviour of sedimentary Fe in CLASS-associated waterways.     

Apparent solubilities of schwertmannite and ferrihydrite in natural stream waters polluted by mine drainage

The apparent solubilities of schwertmannite and ferrihydrite were estimated from the H⁺, OH⁻, Fe³⁺, and SO₄²⁻ activities of the natural stream waters in Korea and mine drainage in Ohio, USA. Both chemical composition of the stream waters and the mineralogy of the precipitates were determined for samples from two streams polluted by coal mine drainage. This study combines these new results with previous data from Ohio, USA to redetermine solubilities. The activities of the dissolved species necessary for the solubility determinations were calculated from the chemical compositions of the waters with the WATEQ4F computer code.Laboratory analyses of precipitates indicated that the main minerals present in Imgok and Osheep creek were schwertmannite and ferrihydrite, respectively. The schwertmannite from Imgok creek had a variable chemical formula of Fe₈O₈(OH)_8−2x(SO₄)_x· nH₂O, where 1.74 ≤ x ≤ 1.86 and 8.17 ≤ n ≤ 8.62. The chemical formula of ferrihydrite was Fe₂O₃· 1.6H₂O. With known mineralogy of the precipitates from each stream, the activities of H⁺, OH⁻, Fe³⁺, and SO₄²⁻ in the waters were plotted on logarithmic activity-activity diagrams to determine apparent solubilities of schwertmannite and ferrihydrite. The best estimate for the logarithm of the solubility product of schwertmannite, logK_s, was 10.5 ± 2.5 around 15°C. This value of logK_s constrains the logarithm of the solubility product of ferrihydrite, logK_f, to be 4.3 ± 0.5 to maintain the stability boundary with schwertmannite observed in natural waters.     

Hydrochemistry of Salt Lakes of the Qinghai-Tibet Plateau, China

The authors have carried out scientific investigations of salt lakes on the Qinghai-Tibet Plateau since 1956 and collected 550 hydrochemical data from various types of salt lakes. On that basis, combined with the tectonic characteristics of the plateau, the hydrochemical characteristics of the salt lakes of the plateau are discussed. The salinity of the lakes of the plateau is closely related to the natural environment of lake evolution, especially the climatic conditions. According to the available data and interpretation of satellite images, the salinity of the lakes of the plateau has a general trend of decreasing from north and northwest to south and southeast, broadly showing synchronous variations with the annual precipitation and aridity (annual evaporation/annual precipitation) of the modern plateau. The pH values of the plateau salt lakes are related to both hydrochemical types and salinities of the lake waters, i.e., the pH values tend to decrease from the carbonate type → sodium sulfate subtype → magnesium sulfate subtype → chloride type; on the other hand, a negative correlation is observed between the pH and salinities of the lakes. Geoscientists and biological limnologists generally use main ions in salt lakes as the basis for the hydrochemical classification of salt lakes. The common ions in salt lakes are Ca²⁺, Mg²⁺, Na⁺, K⁺, Cl^? SO₄ ^2?, CO₃ ^2?, and HCO₃ ^?. In this paper, the Kurnakov-Valyashko classification is used to divide the salt lakes into the chloride type, magnesium sulfate subtype, sodium sulfate subtype and carbonate type, and then according to different total alkalinities (K _C = Na₂CO₃ + NaHCO₃/total salt × 100%) and different saline mineral assemblages, the carbonate type is further divided into three subtypes, namely, strong carbonate subtype, moderate carbonate subtype and weak carbonate subtypes. According to the aforesaid hydrochemical classifications, a complete and meticulous hydrochemical classification of the salt lakes of the plateau has been made and then a clear understanding of the characteristics of N–S hydrochemical zoning and E-W hydrochemical differentiation has been obtained. The plateau is divided into four zones and one area. There is a genetic association between certain saline minerals and specific salt lake hydrochemical types: the representative mineral assemblages of the carbonate type of salt lake is borax (tincalconite) and borax-zabuyelite (L₂CO₃) and alkali carbonate-mirabilite; the representative mineral assemblages of the sodium sulfate subtype are mirabilite (thenardite)-halite and magnesium borate (kurnakovite, inderite etc.)-ulexite-mirabilite; the representative mineral assemblages of the magnesium sulfate subtype are magnesium sulfate (epsomite, bloedite)-halite, magnesium borate-mirabilite, and mirabilite-schoenite-halite, as well as large amount of gypsum; The representative mineral assemblages of the chloride type are carnallite-bischofite-halite and carnallite-halite, with antarcticite in a few individual salt lakes. The above-mentioned salt lake mineral assemblages of various types on the plateau have features of cold-phase assemblages. Mirabilite and its associated cold-phase saline minerals are important indicators for the study of paleoclimate changes of the plateau. A total of 59 elements have been detected in lake waters of the plateau now, of which the concentrations of Na, K, Mg, Ca, and Cl, and SO₄ ^2?, CO₃ ^2?, and HCO₃ ^? ions are highest, but, compared with the hydrochemical compositions of other salt lake regions, the plateau salt lakes, especially those in the southern Qiangtang carbonate type subzone (I₂), contain high concentrations of Li, B, K, Cs, and Rb, and there are also As, U, Th, Br, Sr, and Nd positive anomalies in some lakes. In the plateau lake waters, B is intimately associated with Li, Cs, K and Rb and its concentration shows a general positive correlation with increasing salinity of the lake waters. The highest positive anomalies of B, Li, Cs, and K center on the Ngangla Ringco Lake area in the western segment of the southern Qiangtang carbonate type subzone (I₂) and coincide with Miocene volcanic-sedimentary rocks and high-value areas of B, Li, and Cs of the plateau. This strongly demonstrates that special elements such as B, Li, and Cs on the plateau were related to deep sources. Based on recent voluminous geophysical study and geochemical study of volcanic rocks, their origin had close genetic relation to anatectic magmatism resulting from India–Eurasia continent–continent collision, and B–Li (-Ce) salt lakes in the Cordillera Plateau of South America just originated on active continental margins, both of which indicate that global specific tectonically active belts are the main cause for the high abundances of B, Li, and Cs (K and Rb) in natural water and mineralization of these elements.     

Reductive transformation of iron and sulfur in schwertmannite-rich accumulations associated with acidified coastal lowlands

We examined the transformations of Fe and S associated with schwertmannite (Fe₈O₈(OH)₆SO₄) reduction in acidified coastal lowlands. This was achieved by conducting a 91 day diffusive-flux column experiment, which involved waterlogging of natural schwertmannite- and organic-rich soil material. This experiment was complemented by short-term batch experiments utilizing synthetic schwertmannite. Waterlogging readily induced bacterial reduction of schwertmannite-derived Fe(III), producing abundant pore-water Fe^II, SO₄ and alkalinity. Production of alkalinity increased pH from pH 3.4 to pH ∼6.5 within the initial 14 days, facilitating the precipitation of siderite (FeCO₃). Interactions between schwertmannite and Fe^II at pH ∼6.5 were found, for the first time, to catalyse the transformation of schwertmannite to goethite (αFeOOH). Thermodynamic calculations indicate that this Fe^II-catalysed transformation shifted the biogeochemical regime from an initial dominance of Fe(III)-reduction to a subsequent co-occurrence of both Fe(III)- and SO₄-reduction. This lead firstly to the formation of elemental S via H₂S oxidation by goethite, and later also to formation of nanoparticulate mackinawite (FeS) via H₂S precipitation with Fe^II. Pyrite (FeS₂) was a quantitatively insignificant product of reductive Fe and S mineralization. This study provides important new insights into Fe and S geochemistry in settings where schwertmannite is subjected to reducing conditions.     

Geochemistry and stable isotope investigation of acid mine drainage associated with abandoned coal mines in central Montana,USA

The Great Falls-Lewistown Coal Field (GFLCF) in central Montana contains over 400 abandoned underground coal mines, many of which are discharging acidic water with serious environmental consequences. Areas of the mines that are completely submerged by groundwater have circum-neutral pH and relatively low concentrations of metals, whereas areas that are only partially flooded or freely draining have acidic pH (< 3) and high concentrations of metals. The pH of the mine drains either decreases or increases after discharging to the surface, depending on the initial ratio of acidity (mainly Al and Fe²⁺) to alkalinity (mainly HCO₃^?). In acidic, Fe-rich waters, oxidation of Fe²⁺ after exposure to air is microbially catalyzed and follows zero-order kinetics, with computed rate constants falling in the range of 0.97 to 1.25 mmol L^? 1 h^? 1. In contrast, Fe²⁺ oxidation in near-neutral pH waters appears to be first-order with respect to Fe²⁺ concentration, although insufficient data were collected to constrain the rate law expression. Rates of Fe²⁺ oxidation in the field are dependent on temperature such that lower Fe²⁺ concentrations were measured in down-gradient waters during the day, and higher concentrations at night. Diel cycles in dissolved concentrations of Zn and other trace metals (Mn, Ni) were also noted for down-gradient waters that were net alkaline, but not in the acidic drains.The coal seams of the GFLCF and overlying Cretaceous sandstones form a perched aquifer that lies ~ 50 m above the regional water table situated in the underlying Madison Limestone. The δD and δ¹⁸O values of flooded mine waters suggest local derivation from meteoric water that has been partially evaporated in agricultural soils overlying the coal mines. The S and O isotopic composition of dissolved sulfate in the low pH mine drains is consistent with oxidation of biogenic pyrite in coal under aerated conditions. A clear distinction exists between the isotopic composition of sulfate in the acid mine waters and sulfate in the adjacent sedimentary aquifers, making it theoretically possible to determine if acid drainage from the coal mines has leaked into the underlying Madison aquifer.     

Electronic structures of iron(III) and manganese(IV) (hydr)oxide minerals: Thermodynamics of photochemical reductive dissolution in aquatic environments

Sunlight-induced reduction and dissolution of colloidal Fe-Mn (hydr)oxide minerals yields elevated concentrations of Fe²⁺ and Mn²⁺ in natural waters. Since these elements may be biolimiting micronutrients, photochemical reactions might play a significant role in biogeochemical cycles. Reductive photodissolution of Fe (hydr)oxide minerals may also release sorbed metals. The reactivity of Fe-Mn (hydr)oxide minerals to sunlight-induced photochemical dissolution is determined by the electronic structure of the mineral-water interface. In this work, oxygen K-edge absorption and emission spectra were used to determine the electronic structures of iron(III) (hydr)oxides (hematite, goethite, lepidocrocite, akaganeite and schwertmannite) and manganese(IV) oxides (pyrolusite, birnessite, cryptomelane). The band gaps in the iron(III) (hydr)oxide minerals are near 2.0-2.5 eV; the band gaps in the manganese (IV) oxide phases are 1.0-1.8 eV. Using published values for the electrochemical flat-band potential for hematite together with experimental pH_pzc values for the (hydr)oxides, it is possible to predict the electrochemical potentials of the conduction and valence bands in aqueous solutions as a function of pH. The band potentials enable semiquantitative predictions of the susceptibilities of these minerals to photochemical dissolution in aqueous solutions. At pH 2 (e.g., acid-mine waters), photoreduction of iron(III) (hydr)oxides could yield millimolal concentrations of aqueous Fe²⁺ (assuming surface detachment of Fe²⁺ is not rate limiting). In seawater (pH 8.3), however, the direct photo-reduction of colloidal iron(III) (hydr)oxides to give nanomolal concentrations of dissolved, uncomplexed, Fe²⁺ is not thermodynamically feasible. This supports the hypothesis that the apparent photodissolution of iron(III) (hydr)oxides in marines systems results from Fe³⁺ reduction by photochemically produced superoxide. In contrast, the direct photoreduction of manganese oxides should be energetically feasible at pH 2 and 8.3.     

Assessing mine drainage pH from the color and spectral reflectance of chemical precipitates

The pH of mine impacted waters was estimated from the spectral reflectance of resident sediments composed mostly of chemical precipitates. Mine drainage sediments were collected from sites in the Anthracite Region of eastern Pennsylvania, representing acid to near neutral pH. Sediments occurring in acidic waters contained primarily schwertmannite and goethite while near neutral waters produced ferrihydrite. The minerals comprising the sediments occurring at each pH mode were spectrally separable. Spectral angle difference mapping was used to correlate sediment color with stream water pH (r²=0.76). Band-center and band-depth analysis of spectral absorption features were also used to discriminate ferrihydrite and goethite and/or schwertmannite by analyzing the ⁴T₁←⁶A₁ crystal field transition (900–1000 nm). The presence of these minerals accurately predicted stream water pH (r²=0.87) and provided a qualitative estimate of dissolved SO₄ concentrations. Spectral analysis results were used to analyze airborne digital multispectral video (DMSV) imagery for several sites in the region. The high spatial resolution of the DMSV sensor allowed for precise mapping of the mine drainage sediments. The results from this study indicate that airborne and space-borne imaging spectrometers may be used to accurately classify streams impacted by acid vs. neutral-to-alkaline mine drainage after appropriate spectral libraries are developed.     

Mineral species control of aluminum solubility in sulfate-rich acidic waters

The identification of the mineral species controlling the solubility of Al in acidic waters rich in sulfate has presented researchers with several challenges. One of the particular challenges is that the mineral species may be amorphous by X-ray diffraction. The difficulty in discerning between adsorbed or structural sulfate is a further complication. Numerous studies have employed theoretical calculations to determine the Al mineral species forming in acid sulfate soil environments. The vast majority of these studies indicate the formation of a mineral species matching the stoichiometry of jurbanite, Al(OH)SO₄·5H₂O. Much debate, however, exists as to the reality of jurbanite forming in natural environments, particularly in view of its apparent rare occurrence. In this work the use of Al, S and O K-edge XANES spectroscopy, in combination with elemental composition analyses of groundwater precipitates and a theoretical analysis of soluble Al concentrations ranging from pH 3.5 to 7, were employed to determine the mineral species controlling the solubility of Al draining from acid sulfate soils into Blacks Drain in north-eastern New South Wales, Australia. The results indicate that a mixture of amorphous Al hydroxide (Al(OH)₃) and basaluminite (Al₄(SO₄)(OH)₁₀·5H₂O) was forming. The use of XANES spectroscopy is particularly useful as it provides insight into the nature of the bond between sulfate and Al, and confirms the presence of basaluminite. This counters the possibility that an Al hydroxide species, with appreciable amounts of adsorbed sulfate, is forming within these groundwaters.Below approximately pH 4.5, prior to precipitation of this amorphous Al(OH)₃/basaluminite mixture, our studies indicate that the Al³⁺ activity of these acidic sulfate-rich waters is limited by the availability of dissolved Al from exchangeable and amorphous/poorly crystalline mineral species within adjacent soils. Further evidence suggests the Al³⁺ activity below pH 4.5 is then further controlled by dilution with either rainwater or pH 6-8 buffered estuarine water, and not a notional Al(OH)SO₄ mineral species.     

Seasonal variations of ochreous precipitates in mine effluents in Finland

Ochreous precipitate and water samples were collected from the surroundings of seven closed sulphide mines in Finland. In the Hammaslahti Zn–Cu–Au mine, Otravaara pyrite mine and Paroistenjärvi Cu–W–As mine, the collection was repeated in different seasons to study mineralogical and geochemical variations of precipitates. The sampling was done in 1999–2002 from the ditches and drainage ponds of the tailings and waste rock piles that are susceptible to seasonal changes. Mineralogy of the precipitates was evaluated by X-ray diffraction (XRD) and infrared spectroscopy (IR), and precipitate geochemistry was examined by selective extractions. Schwertmannite (Fe₈O₈(OH)₆SO₄) was the most typical Fe hydroxide mineral found. Goethite was almost as common as schwertmannite, was often poorly ordered, and contained up to 10 wt.% of SO₄. Goethite and schwertmannite were commonly found as mixtures, and they occurred in similar pH and SO₄ concentrations. Ferrihydrite (nominally Fe₅HO₈ · 4H₂O) was typically found in areas not influenced by acid mine drainage, and also in acid mine waters with high organic matter or As content. Jarosite (KFe₃(SO₄)₂(OH)₆) was found only in one site. In addition, some gypsum (CaSO₄ · 2H₂O) and aluminous sulphate precipitates (presumably basaluminite, Al₄(SO₄)(OH)₁₀ · 5H₂O) were identified. Selective extractions showed that acid extracts Fe_tot/S_tot-ratios of schwertmannite and goethite samples were similar, but the ratio of oxalate-extractable to total Fe, Fe_ox/Fe_tot, of goethite samples were lower than those of the schwertmannite samples. Only Al, Si and As were bound to precipitates in substantial amounts, up to several wt.%. In schwertmannites and goethites, Al, Cu, Co, Mn and Zn were mostly structural, substituting for Fe in an Fe oxyhydroxide structure or bound to surface adsorption sites in pores limited by diffusion. In ferrihydrites, heavy metals were also partly bound in adsorbed form dissolving in acid ammonium acetate. Ferrihydrites and goethites were more enriched in Co, Mn and Zn than schwertmannites, but schwertmannites and ferrihydrites were more enriched in As than goethites. Mineralogical and geochemical evidence showed that in the spring, after the snowmelt, the acid mine drainage precipitates were predominantly schwertmannite, and were partly transformed during warm summer months to goethite. The phase transformation of precipitates was followed by a decrease in pH values and increase in SO₄ concentrations of waters. Adsorbed As retarded the phase transformation.     

Photoreduction of Fe(III) in the Acidic Mine Pit Lake of San Telmo (Iberian Pyrite Belt): Field and Experimental Work

Light-induced reduction of dissolved and particulate Fe(III) has been observed to occur in the surface waters of the acidic mine pit lake of San Telmo (143,600 m², pH 2.8, Fe_total = 2.72 mM). This photochemical production of Fe(II) is directly related to the intensity of solar radiation and competes with biologically catalyzed reactions (i.e., bacterial re-oxidation of Fe(II)) and physical processes (including ionic diffusion, advection, and convection, which tend to homogenize the epilimnetic concentration of Fe(II) at every moment). Therefore, diel cycles of Fe(II) concentration are observed at the lake surface, with minimum values of 10–20 μM Fe(II) (0.35–0.70% Fe_total) at the sunrise and sunset, and maximum values of 90 μM Fe(II) (3.2% Fe_total) at midday in August 2005. Field and experimental work conducted in San Telmo and other pit lakes of the Iberian Pyrite Belt (IPB) (pH 2.3–3.1, Fe_total = 0.34–17 mM) indicate that the kinetics of the photoreductive reaction is zero-order and is independent of the Fe(III) concentration, but highly dependent on the intensity of solar radiation and temperature. Experimental work conducted with natural Fe(III) minerals (schwertmannite, goethite, and lepidocrocite) suggests that dissolved organic matter is an important factor contributing to the photochemical production of Fe(II). The wavelengths involved in the photoreduction of Fe(III) include not only the spectrum of UV-A radiation (315–400 nm), but also part of the photosynthetically active radiation (PAR, 400–700 nm). This finding is of prime importance for the understanding of the photoreduction processes in the pit lakes of the IPB, because the photo-reactive depth is not limited to the penetration depth of UV-A radiation (upper 1–10 cm of the water column depending on the TDS content), but it is approximately equal to the penetration depth of PAR (e.g., first 4–6 m of the water column in San Telmo on July 2007); thus, increasing the importance of photochemical processes in the hydro(bio)geochemistry of pit lakes.     

Screening Effect of the Diffusive Boundary Layer in Sediments of Lake Aha in the Suburbs of Guiyang City,Guizhou Province

The redox cycle of iron and manganese is a major geochemica process at the boundary layers of lake sediments.Lake Aha,which lies in the suburbs of Guiyang City,Guizhou Province,China,is a medium-sized artificial reservoir with seasonally anoxic hypolimnion,Long-term sedimentary accumulation of iron and manganese resulted in their enrichment in the upper sediments,In the anoxic season,Fe^2 and Mn^2 ,formed by diological oxidation,would diffuse up to overlying waters from sediments.However,the concentration of oxidation,would diffuse up to overlying waters from sediments,However,the concentration of Fe^2 increased later and decreased earlier than that of Mn^2 .Generally,sulfate reduction occurred at 6 cm below the sediment-water interface.Whereas,in the anoxic season.the reduction reached upper sediments,inhibiting the release of Fe^2 ,The Fe concentration of anoxic water is quickly decreased from high to low as a result of reduction of the suplhur system.     

Iron sulfide oxidation and the chemistry of acid generation

Acid mine drainage, produced from the oxidation of iron sulfides, often contains elevated levels of dissolved aluminum (AI), iron (Fe), and sulfate (SO₄) and low pH. Understanding the interactions of these elements associated with acid mine drainage is necessary for proper solid waste management planning. Two eastern oil shales were leached using humidity cell methods. This study used a New Albany Shale (4.6 percent pyrite) and a Chattanooga Shale (1.5 percent pyrite). The leachates from the humidity cells were filtered, and the filtrates were analyzed for total concentrations of cations and anions. After correcting for significant solution species and complexes, ion activities were calculated from total concentrations. The results show that the activities of Fe³⁺, Fe²⁺, Al³⁺, and SO₄ ²⁻ increased due to the oxidation of pyrite. Furthermore, the oxidation of pyrite resulted in a decreased pH and an increased pe+pH (redox-potential). The Fe³⁺ and Fe²⁺ activities appeared to be controlled by amorphous Fe(OH)₃ solid phase above a pH of 6.0 and below pe+pH 11.0. The Fe³⁺, Fe²⁺, and SO₄ ²⁻ activities reached saturation with respect to FeOHSO₄ solid phase between pH 3.0 and 6.0 and below pe+pH 11.0 Below a pH of 3.0 and above a pe+pH of 11.0, Fe²⁺, Fe³⁺, and SO₄ ²⁻ activities are supported by FeSO₄·7H₂O solid phase. Above a pH of 6.0, the Al³⁺ activity showed an equilibrium with amorphous Al(OH)₃ solid phase. Below pH 6.0, Al³⁺ and SO₄ ²⁻ activities are regulated by the AlOHSO₄ solid phase, irrespective of pe+pH. The results of this study suggest that under oxidizing conditions with low to high leaching potential, activities of Al and Fe can be predicted on the basis of secondary mineral formation over a wide range of pH and redox. As a result, the long-term chemistry associated with disposal environments can be largely predicted (including trace elements).     

The structure and transformation of the nanomineral schwertmannite: a synthetic analog representative of field samples

The phase transformation of schwertmannite, an iron oxyhydroxide sulfate nanomineral synthesized at room temperature and at 75 °C using H₂O₂ to drive the precipitation of schwertmannite from ferrous sulfate (Regenspurg et al. in Geochim Cosmochim Acta 68:1185–1197, 2004), was studied using high-resolution transmission electron microscopy. The results of this study suggest that schwertmannite synthesized using this method should not be described as a single phase with a repeating unit cell, but as a polyphasic nanomineral with crystalline areas spanning less than a few nanometers in diameter, within a characteristic ‘pin-cushion’-like amorphous matrix. The difference in synthesis temperature affected the density of the needles on the schwertmannite surface. The needles on the higher-temperature schwertmannite displayed a dendritic morphology, whereas the needles on the room-temperature schwertmannite were more closely packed. Visible lattice fringes in the schwertmannite samples are consistent with the powder X-ray diffraction (XRD) pattern taken on the bulk schwertmannite and also matched d-spacings for goethite, indicating a close structural relationship between schwertmannite and goethite. The incomplete transformation from schwertmannite to goethite over 24 h at 75 °C was tracked using XRD and TEM. TEM images suggest that the sample collected after 24 h consists of aggregates of goethite nanocrystals. Comparing the synthetic schwertmannite in this study to a study on schwertmannite produced at 85 °C, which used ferric sulfate, reveals that synthesis conditions can result in significant differences in needle crystal structure. The bulk powder XRD patterns for the schwertmannite produced using these two samples were indistinguishable from one another. Future studies using synthetic schwertmannite should account for these differences when determining schwertmannite’s structure, reactivity, and capacity to take up elements like arsenic. The schwertmannite synthesized by the Regenspurg et al. method produces a mineral that is consistent with the structure and morphology of natural schwertmannite observed in our previous study using XRD and TEM, making this an ideal synthetic method for laboratory-based mineralogical and geochemical studies that intend to be environmentally relevant.     

A.ferrooxidans培养过程中Al/Fe(摩尔比)对铁矿物形成产物的影响

主要研究了磷酸铝(Al PO4)的加入量对氧化亚铁硫杆菌HX3培养液中铁矿物形成的影响,并对相应沉淀产物进行了结构表征分析。结果表明,Al PO4的加入对细菌培养过程中Fe2+的氧化无明显影响,但可促进Fe3+的水解和初始铁矿物相的形成,也可加速黄钾铁矾的转化形成。Al/Fe(摩尔比)为0. 04～1的培养液中主要形成产物为施威特曼石和黄钾铁矾; Al/Fe为0. 4和1时另有磷酸铁矿形成。较高的Al/Fe比值和磷酸根含量有利于磷酸铁矿的形成。     

Abundance and fractionation of Al,Fe and trace metals following tidal inundation of a tropical acid sulfate soil

Tidal inundation was restored to a severely degraded tropical acid sulfate soil landscape and subsequent changes in the abundance and fractionation of Al, Fe and selected trace metals were investigated. After 5 a of regular tidal inundation there were large decreases in water-soluble and exchangeable Al fractions within former sulfuric horizons. This was strongly associated with decreased soil acidity and increases in pH, suggesting pH-dependent immobilisation of Al via precipitation as poorly soluble phases. The water-soluble fractions of Fe, Zn, Ni and Mn also decreased. However, there was substantial enrichment (2–5×) of the reactive Fe fraction (Fe_R; 1 M HCl extractable) near the soil surface, plus a closely corresponding enrichment of 1 M HCl extractable Cr, Zn, Ni and Mn. Surficial accumulations of Fe(III) minerals in the inter-tidal zone were poorly crystalline (up to 38% Fe_R) and comprised mainly of schwertmannite (Fe₈O₈(OH)₆SO₄) with minor quantities of goethite (α-FeOOH) and lepidocrocite (γ-FeOOH). These Fe (III) mineral accumulations provide an effective substrate for the adsorption/co-precipitation and accumulation of trace metals. Arsenic displayed contrary behaviour to trace metals with peak concentrations (∼60 μg g⁻¹) near the redox minima. Changes in the abundance and fractionation of the various metals can be primarily explained by the shift in the geochemical regime from oxic–acidic to reducing-circumneutral conditions, combined with the enrichment of reactive Fe near the soil surface. Whilst increasing sequestration of trace metals via sulfidisation is likely to occur over the long-term, the current abundance of reactive Fe near the sediment–water interface favours a dynamic environment with respect to metals in the tidally inundated areas.     

The solubility control of rare earth elements in natural terrestrial waters and the significance of PO 4 3− and CO 3 2− in limiting dissolved rare earth concentrations: A review of recent information

Rare earth element (REE) concentrations in alkaline lakes, circumneutral pH groundwaters, and an acidic freshwater lake were determined along with the free carbonate, free phosphate, and free sulfate ion concentrations. These parameters were used to evaluate the saturation state of these waters with respect to REE phosphate and carbonate precipitates. Our activity product estimates indicate that the alkaline lake waters and groundwaters are approximately saturated with respect to the REE phosphate precipitates but are significantly undersaturated with respect to REE carbonate and sulfate precipitates. On the other hand, the acidic lake waters are undersaturated with respect to REE sulfate, carbonate, and phosphate precipitates. Although carbonate complexes tend to dominate the speciation of the REEs in neutral and alkaline waters, our results indicate that REE phosphate precipitates are also important in controlling REE behavior. More specifically, elevated carbonate ion concentrations in neutral to alkaline natural waters tend to enhance dissolved REE concentrations through the formation of stable REE-carbonate complexes whereas phosphate ions tend to lead to the removal of the REEs from solution in these waters by the formation of REE-phosphate salts. Removal of REEs by precipitation as phosphate phases in the acid lake (pH=3.6) is inconsequential, however, due to extremely low [PO ₄ ^3– ] _F concentrations (i.e., 10^–23 mol/kg).     

Solubility relationships of aluminum and iron minerals associated with acid mine drainage

The ability to properly manage the oxidation of pyritic minerals and associated acid mine drainage is dependent upon understanding the chemistry of the disposal environment. One accepted disposal method is placing pyritic-containing materials in the groundwater environment. The objective of this study was to examine solubility relationships of Al and Fe minerals associated with pyritic waste disposed in a low leaching aerobic saturated environment. Two eastern oil shales were used in this oxidizing equilibration study, a New Albany Shale (unweathered, 4.6 percent pyrite), and a Chattanooga Shale (weathered, 1.5 percent pyrite). Oil shale samples were equilibrated with distilled-deionized water from 1 to 180 d with a 1∶1 solid-to-solution ratio. The suspensions were filtered and the clear filtrates were analyzed for total cations and anions. Ion activities were calculated from total concentrations. Below pH 6.0, depending upon SO ₄ ²⁻ activity, Al³⁺ solubility was controlled by AlOHSO₄ (solid phase) for both shales. Initially, Al³⁺ solubility for the New Albany Shale showed equilibrium with amorphous Al(OH)₃. The pH decreased with time, and Al³⁺ solubility approached equilibrium with AlOHSO_4(s). Below pH 6.0, Fe³⁺ solubility appeared to be regulated by a basic iron sulfate solid phase with the stoichiometric composition of FeOHSO_4(s). The results of this study indicate that below pH 6.0, Al³⁺ solubilities, are limited by basic Al and Fe sulfate solid phases (AlOHSO_4(s) and FeHSO_4(s)). The results from this study further indicate that the acidity in oil shale waters is produced from the hydrolysis of Al³⁺ and Fe³⁺ activities in solution. These results indicate a fundamental change in the stoichiometric equations used to predict acidity from iron sulfide oxidation. The results of this study also indicate that water quality predictions associated with acid mine drainage can be based on fundamental thermodynamic relationships. As a result, waste management decisions can be based on waste-specific/site-specific test methods.     

Modeling ferrous-ferric iron chemistry with application to martian surface geochemistry

The Mars Global Surveyor, Mars Exploration Rover, and Mars Express missions have stimulated considerable thinking about the surficial geochemical evolution of Mars. Among the major recent mission findings are the presence of jarosite (a ferric sulfate salt), which requires formation from an acid-sulfate brine, and the occurrence of hematite and goethite on Mars. Recent ferric iron models have largely focused on 25 °C, which is a major limitation for models exploring the geochemical history of cold bodies such as Mars. Until recently, our work on low-temperature iron-bearing brines involved ferrous but not ferric iron, also obviously a limitation. The objectives of this work were to (1) add ferric iron chemistry to an existing ferrous iron model (FREZCHEM), (2) extend this ferrous/ferric iron geochemical model to lower temperatures (<0 °C), and (3) use the reformulated model to explore ferrous/ferric iron chemistries on Mars.The FREZCHEM model is an equilibrium chemical thermodynamic model parameterized for concentrated electrolyte solutions using the Pitzer approach for the temperature range from <−70 to 25 °C and the pressure range from 1 to 1000 bars. Ferric chloride and sulfate mineral parameterizations were based, in part, on experimental data. Ferric oxide/hydroxide mineral parameterizations were based exclusively on Gibbs free energy and enthalpy data. New iron parameterizations added 23 new ferrous/ferric minerals to the model for this Na-K-Mg-Ca-Fe(II)-Fe(III)-H-Cl-SO₄-NO₃-OH-HCO₃-CO₃-CO₂-O₂-CH₄-H₂O system.The model was used to develop paragenetic sequences for Rio Tinto waters on Earth and a hypothetical Martian brine derived from acid weathering of basaltic minerals. In general, model simulations were in agreement with field evidence on Earth and Mars in predicting precipitation of stable iron minerals such as jarosites, goethite, and hematite. In addition, paragenetic simulations for Mars suggest that other iron minerals such as lepidocrocite, schwertmannite, ferricopiapite, copiapite, and bilinite may also be present on the surface of Mars. Evaporation or freezing of the Martian brine led to similar mineral precipitates. However, in freezing, compared to evaporation, the following key differences were found: (1) magnesium sulfates had higher hydration states; (2) there was greater total aqueous sulfate (SO_4T = SO₄ + HSO₄) removal; and (3) there was a significantly higher aqueous Cl/SO_4T ratio in the residual Na-Mg-Cl brine. Given the similarities of model results to observations, alternating dry/wet and freeze/thaw cycles and brine migration could have played major roles in vug formation, Cl stratification, and hematite concretion formation on Mars.     

Chemistry and mineralogy of ochreous sediments in a constructed mine drainage wetland

The objective of this study was to examine the mineralogy and geochemical stability of ochreous sediments accumulated in a compost wetland constructed in 1990 for acid mine drainage treatment. Intact sediment cores were collected in 1996 and 2000 from an area that had accumulated 33 cm of ochre. Solids and pore waters were subsequently separated by centrifugation and analyzed using conventional methods, including X-ray diffraction, infrared spectroscopy, scanning electron microscopy, and wet chemical techniques. The solid phase had an average Fe content of 585 g/kg and was predominantly schwertmannite [Fe ₈O₈(OH)_4.8(SO₄)_1.6] in the upper portion of the sediment column, but transformed to goethite (α-FeOOH) with depth. The rate of transformation was calculated to be 30 mol/m³/yr in the initial 6 yr of sedimentation as compared to 10 mol/m³/yr for the 4-yr period from 1996 to 2000. Pore water composition was affected by this mineral transformation through production of acidity and the release of Fe and SO₄. These results demonstrate that the sediment column was not a static environment. In addition, the transformation of schwertmannite to goethite, which has been observed under laboratory conditions, also occurs in natural systems.